The present invention relates to products, including preservative systems and compositions comprising such preservative systems (e.g., foods, beverages, health care products, personal care products, herbicidal products, and containment devices which incorporate the foregoing preservative system). The products comprise a constituent comprising one or more isothiocyanate compounds. The present invention further relates to methods of preserving products comprising utilizing the foregoing preservative systems.
Consumer products can provide a hospitable environment for rapid microbial growth. Such exposure can, and frequently does, result from inadvertent microbial inoculation of the product during manufacturing or packaging. Spoilage microorganisms, for example in food or beverage products, can then rapidly proliferate by feeding on nutrients provided by the product.
Preservatives, such as sorbates, benzoates, organic acids, and combinations thereof have been used in various products, particularly foods and beverages, to provide some degree of microbial inhibition. At levels effective to inhibit microbial growth, some of these preservatives can contribute off-flavors in the product, thus making the product undesirable for its intended purpose. For example, accepted usage levels for potassium sorbate is typically in the range of from about 200 ppm to about 3000 ppm. However, at the higher end of this accepted usage range, potassium sorbate can contribute to off-flavors in the foods or beverages.
Additionally, certain preservative systems are not effective in the presence of fortification components, including various vitamins and minerals. For example, calcium fortification in certain food or beverage products can render the preservative system inactive, thereby failing to inhibit microbial growth. Therefore, wherein nutrient fortification is desirable, expensive preservative components such as dimethyl dicarbonate (DMDC) must be utilized to inhibit microbial growth in the fortified product.
It has been disclosed that oil of mustard, which contains isothiocyanates, exhibits an antibacterial and antimycotic effect in oral therapies and on certain foods. See e.g., Sekiyama et al., U.S. Pat. No. 5,334,373, assigned to Nippon Sanso Corp., issued Aug. 2, 1994; and Madaus et al., U.S. Pat. No. 3,998,964, issued Dec. 21, 1976. However, it has been suggested that mustard oil can irritate the mucous membranes and may not be well tolerated by individuals ingesting the oil. See e.g., Madaus et al. Additionally, mustard oil can exhibit strong characteristic flavors which render the oil unfavorable for use in food or beverage products. Accordingly, mustard oil has not been widely known or widely utilized in the art for its antibacterial and antimycotic effect, particularly in products suitable for ingestion such as food and beverage products.
However, the present inventors have surprisingly discovered that one or more isothiocyanate compounds, optionally in combination with a sorbate and/or benzoate preservative, exhibits a strong antimicrobial effect without imparting off-flavors or offensive odors in the final product. In doing so, the present inventors have discovered a synergistic relationship between the relative effects of each of the preservative components when utilized in combination. Surprisingly, when utilized in combination, each of the preservative components are effective at levels low enough to maintain the organoleptic integrity of the final food or beverage product. The present inventors have further surprisingly discovered that such antimicrobial effect is maintained even in the presence of fortification nutrients such as calcium, thus overcoming the problems associated with currently fortified products. Accordingly, the preservative systems of the present invention are utilized at relatively low levels, provides maintenance of flavor and odor integrity, and are effective against microbial growth even in the presence of fortification nutrients.
The present invention relates to products comprising the following preservative system:
(a) a constituent comprising one or more isothiocyanate compounds; and
(b) a preservative selected from sorbate preservatives, benzoate preservatives, and mixtures thereof.
The present invention further relates to methods of preserving a product comprising incorporating the foregoing preservative system into the product.
The present invention further relates to beverage products comprising:
(a) a constituent comprising one or more isothiocyanate compounds; and
(b) a beverage member selected from the group consisting of water, fruit juice, tea solids, milk solids, fruit flavors, botanical flavors, and mixtures thereof.
The present invention further relates to methods of preserving a beverage product comprising incorporating one or more isothiocyanate compounds into the beverage product.
In accordance with the present invention, the products may be preservative systems suitable for incorporation into various compositions requiring an antimicrobial effect. Additionally, the products may be compositions exhibiting an antimicrobial effect including, for example, food products, beverage products (including, e.g., ready-to-drink products and concentrates), health care products (including, e.g., oral care products), personal care products, herbicidal products, and containment devices.
The present invention relates to products providing an antimicrobial effect as well as methods of their use.
Publications and patents are referred to throughout this disclosure. All references cited herein are hereby incorporated by reference.
All percentages, ratios, and proportions used herein are by weight unless otherwise specified.
In the description of the invention various embodiments and/or individual features are disclosed. As will be apparent to the ordinarily skilled practitioner all combinations of such embodiments and features are possible and can result in preferred executions of the invention.
The products herein may comprise, consist essentially of, or consist of any of the elements as described herein.
The following is a list of definitions for terms used herein:
As used herein, xe2x80x9calkenylxe2x80x9d is an unsaturated hydrocarbon straight, branched, or cyclic chain radical. Preferably, the alkenyl is a straight or branched chain radical, most preferably straight. Alkenyls have at least one olefinic double bond. Unless otherwise specified, alkenyls have from 2 to about 15 carbon atoms (C2-C15); preferably from 2 to about 10 carbon atoms (C2-C10); more preferably from 2 to about 8 carbon atoms (C2-C8), even more preferably from about 2 to about 6 carbon atoms (C2-C6), and most preferably from about 2 to about 4 carbon atoms (C2-C4). Non-limiting examples of alkenyls include vinyl, allyl, and butenyl (e.g., 3-butenyl). Alkenyls may be substituted or unsubstituted.
As used herein, xe2x80x9calkoxyxe2x80x9d is an oxygen radical having an alkyl, alkenyl, or alkynyl, preferably an alkyl or alkenyl, and most preferably an alkyl substituent. Examples of alkoxy radicals include xe2x80x94O-alkyl and xe2x80x94O-alkenyl. An alkoxy radical may be substituted or unsubstituted.
As used herein, xe2x80x9calkylxe2x80x9d is a saturated hydrocarbon straight, branched, or cyclic chain radical. Preferably, the alkyl is a straight or branched chain radical, most preferably straight. Unless otherwise specified, alkyls have from 1 to about 15 carbon atoms (C1-C15); preferably from 1 to about 10 carbon atoms (C1-C10); more preferably from 1 to about 6 carbon atoms (C1-C6); and most preferably from 1 to about 4 carbon atoms (C1-C4). Preferred alkyls include, for example, methyl, ethyl, propyl, iso-propyl, and butyl. Alkyls may be substituted or unsubstituted.
As used herein, xe2x80x9calkylarylxe2x80x9d is an alkyl radical substituted with an aryl group or an aryl radical substituted with an alkyl group. Preferred alkylaryl groups include benzyl, phenylethyl, and phenylpropyl. Arylalkyls may be substituted or unsubstituted.
As used herein, xe2x80x9calkynylxe2x80x9d is an unsaturated hydrocarbon straight, branched, or cyclic chain radical. Preferably, the alkynyl is a straight or branched chain radical, most preferably straight. Alkynyls have at least one triple bond. Unless otherwise specified, alkynyls have from 2 to about 15 carbon atoms (C2-C15); preferably from 2 to about 10 carbon atoms (C2-C10); more preferably from 2 to about 8 carbon atoms (C2-C8), even more preferably from about 2 to about 6 carbon atoms (C2-C6), and most preferably from about 2 to about 4 carbon atoms (C2-C4). Alkynyls may be substituted or unsubstituted.
As used herein, xe2x80x9carylxe2x80x9d is an aromatic ring radical which is either carbocyclic or heterocyclic. Preferred aryl groups include, for example, phenyl, benzyl, tolyl, xylyl, cumenyl, napthyl, biphenyl, thienyl, furyl, pyrrolyl, pyridinyl, pyrazinyl, thiazolyl, pyrimidinyl, quinolinyl, triazolyl, tetrazolyl, benzothiazolyl, benzofuryl, indolyl, indenyl, azulenyl, fluorenyl, anthracenyl, oxazolyl, isoxazolyl, isotriazolyl, imidazolyl, pyraxolyl, oxadiazolyl, indolizinyl, indolyl, isoindolyl, purinyl, quinolizinyl, quinolinyl, isoquinolinyl, cinnolinyl, and the like. Aryls may be substituted or unsubstituted.
As used herein, xe2x80x9cessential oilxe2x80x9d refers to the set of all the compounds that can be distilled from the plant from which the oil is derived and that contributes to the characteristic aroma of that plant. See e.g., H. McGee, On Food and Cooking, Charles Scribner""s Sons, p. 154-157 (1984). In accordance with the present invention, the essential oil preferably originates from a glucosinolate compound which is capable of producing an isothiocyanate compound (for example, through the catalytic hydrolysis of one or more glucosinolates by the enzyme myrosinase) wherein the precursor and enzyme containing plant tissue is homogenized, ground, crushed, pressed, or otherwise damaged.
As used herein xe2x80x9cprecursorxe2x80x9d refers to the set of reactants found in, or originating from, a plant, which when reacted in the presence of a catalyst such as an enzyme, produces an essential oil.
As used herein, xe2x80x9cPPMxe2x80x9d represents xe2x80x9cparts per millionxe2x80x9d, as is commonly known in the art.
As used herein, xe2x80x9ceffective amount of a productxe2x80x9d (or constituent, compound, composition, preservative, or the like) means an amount that is effective to exhibit antimicrobial activity, preferably wherein the antimicrobial activity is inhibiting growth of, eliminating, and/or otherwise decreasing the presence of microbials such as, for example, yeast, bacteria, mold, and fungus, preferably yeast and bacteria. Non-limiting examples of such yeast include Candida tropicalis, Candida albicans, Hansenula anomala, Saccharomyces cerevisiae, Torulaspora delbreuckii, Zygosaccharomyces bailii, and Zygosaccharomyces rouxii. Non-limiting examples of such bacteria including Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Staphylococus epidermidis, Escherichia coli, Salmonella typhimurium, Salmonella enteritidis, Vibrio parahaemolyticus, and Pseudomonas aeruginosa. Non-limiting examples of such mold include Aspergillus niger, Aspergillus flavus, Penicillium islandicum, Penicillium citrinum, Penicillium chrysogenum, Fusarium oxysporum, Fusarium graminearum, Fusarium solani, Alternaria alternata, and Mucor racemosus. 
As defined above and as used herein, substituent groups (e.g., alkyl, alkenyl, alkynyl, aryl, and alkylaryl) may themselves be substituted. Such substitution may be with one or more substituents. Such substituents include those listed in C. Hansch and A. Leo, Substituent Constants for Correlation Analysis in Chemistry and Biology (1979). Preferred substituents include, for example, alkyl, alkenyl, alkoxy, aryl, hydroxy (i.e., xe2x80x94OH), oxo (i.e., doubly-bonded oxygen), nitro (i.e., xe2x80x94NO2), amino (i.e., xe2x80x94NH2), cyano (i.e., xe2x80x94C∉N), halo (i.e., chloro, bromo, fluoro, iodo), thiol (i.e., xe2x80x94SH), thioxo (i.e., doubly-bonded sulfur), alkoxy (i.e., xe2x80x94O-alkyl), alkylthio (i.e., xe2x80x94S-alkyl), sulfoxy (i.e., xe2x80x94Sxe2x95x90O (which is also depicted as xe2x80x94S(O)), and sulfone (i.e., xe2x80x94S(O)2).
The present invention relates to products comprising the following preservative system:
(a) a constituent comprising one or more isothiocyanate compounds; and
(b) a preservative selected from sorbate preservatives, benzoate preservatives, and mixtures thereof. The present invention further relates to methods of preserving a product comprising incorporating the foregoing preservative system into the product.
The present invention further relates to beverage products comprising:
(a) a constituent comprising one or more isothiocyanate compounds; and
(b) a beverage member selected from the group consisting of water, fruit juice, tea solids, milk solids, fruit flavors, botanical flavors, and mixtures thereof. Such beverage products optionally, and preferably, further comprise a preservative selected from the group consisting of sorbate preservatives, benzoate preservatives, and mixtures thereof. The present invention further relates to methods of preserving a beverage product comprising incorporating one or more isothiocyanate compounds into the beverage product.
As used herein, the products may be, but are not limited to, preservative systems or any compositions (e.g., foods, beverages, health care products, personal care products, herbicidal products, and containment devices) in which an antimicrobial effect is desirable. Preferably, the products are food or beverage products, most preferably beverage products. As used herein, the term xe2x80x9cantimicrobial effectxe2x80x9d means that the product inhibits growth of, eliminates, and/or otherwise decreases the presence of microbials such as, for example, yeast, bacteria, mold, and/or fungus, preferably yeast and/or bacteria.
The present inventors have surprisingly discovered that an isothiocyanate compound, in combination with a sorbate or benzoate preservative (such combination being optional but preferable for beverage products), exhibits a strong antimicrobial effect without imparting off-flavors or offensive odors in the final product. In doing so, the present inventors have discovered a synergistic relationship between the relative effects of each of the preservative components when utilized in combination. Surprisingly, when utilized in combination, each the preservative components are effective at levels low enough to maintain the organoleptic integrity of the final food or beverage product.
Additionally, the present inventors have surprisingly discovered that one or more isothiocyanate compounds, together with a beverage member selected from water, fruit juice, tea solids, milk solids, fruit flavors, botanical flavors, and mixtures thereof, provides an antimicrobial effect at levels which do not impart off-flavors or offensive odors.
Constituent Comprising the Isothiocyanate Compound
In accordance with the present invention, the products comprise a constituent comprising one or more isothiocyanate compounds (i.e., a compound bearing a xe2x80x94Nxe2x95x90Cxe2x95x90S moiety), preferably one isothiocyanate compound.
The present inventors have discovered that relatively low levels of the isothiocyanate compound produces the desired antimicrobial effect in the present products and methods. Preferably, the isothiocyanate compound is present in the product at a concentration (i.e., the total concentration of all isothiocyanate compounds comprising the product) of less than about 75 ppm, more preferably less than about 30 ppm, still more preferably less than about 20 ppm, even more preferably less than about 15 ppm, and most preferably less than about 10 ppm.
Even further, the present inventors have surprisingly discovered that the isothiocyanate compound exhibits a synergistic antimicrobial effect in combination with a sorbate or benzoate preservative utilized in the present invention (such combination being optional for beverage products), particularly wherein the isothiocyanate compound and the sorbate or benzoate preservative are utilized in the products and methods at low levels. This synergistic effect is a surprising discovery which allows the use of isothiocyanate compounds, which are known to exhibit unpleasant tastes and smells, in products such as food and beverage products.
The ordinarily skilled artisan will readily understand that, from an organoleptic perspective, more isothiocyanate compound can be tolerated in products intended for ingestion which possess intense flavors, e.g., tomato juice or spicy beverages (e.g., V8(copyright) juice). Conversely, less isothiocyanate compound can be organoleptically tolerated in products intended for ingestion which possess less intense flavors, e.g., citrus juices.
Any compound bearing a xe2x80x94Nxe2x95x90Cxe2x95x90S moiety may be utilized in the present invention. Preferably, the isothiocyanate compound has a molecular weight of less than about 500, preferably less than about 400, more preferably less than about 300, and most preferably less than about 200.
Preferably, at least one isothiocyanate compound is non-volatile. As used herein, the term xe2x80x9cnon-volatilexe2x80x9d means that the respective isothiocyanate is not capable of steam distillation at ambient pressure.
Preferably, at least one of the isothiocyanate compounds utilized in the present products (and most preferably each isothiocyanate compound, independently), has the structure:
xe2x80x94Nxe2x95x90Cxe2x95x90S
wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and alkylaryl. As has been stated herein above, substituent groups (here, R) may be substituted or unsubstituted; the terms xe2x80x9calkylxe2x80x9d, xe2x80x9calkenylxe2x80x9d, xe2x80x9calkynylxe2x80x9d, xe2x80x9carylxe2x80x9d, and xe2x80x9calkylarylxe2x80x9d should each be construed to include both substituted and unsubstituted. Non-limiting examples of substituent groups include alkyl, alkenyl, alkoxy, aryl, hydroxy (i.e., xe2x80x94OH), oxo (i.e., doubly-bonded oxygen), nitro (i.e., xe2x80x94NO2), amino (i.e., xe2x80x94NH2), cyano (i.e., xe2x80x94C∉N), halo (i.e., chloro, bromo, fluoro, iodo), thiol (i.e., xe2x80x94SH), thioxo (i.e., doubly-bonded sulfur), alkoxy (i.e., xe2x80x94O-alkyl), alkylthio (i.e., xe2x80x94Sxe2x80x94alkyl), sulfoxy (i.e., xe2x80x94Sxe2x95x90O (which is also depicted as xe2x80x94S(O)), and sulfone (i.e., xe2x80x94S(O)2).
Non-limiting examples of isothiocyanate compounds include:
(a) allyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, horseradish, mustard (particularly black mustard), turnip, cabbage, brussels sprout, kale, collards, and cauliflower),
(b) 3-butenyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, cabbage, horseradish, mustard, cole crops, turnip, and rutabaga),
(c) benzyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, cress, radish, horseradish, and nasturtium),
(d) 2-butyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, horseradish, cabbage, brussels sprout, cauliflower, mustard, and spinach),
(e) p-hydroxybenzyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, mustard (particularly white mustard) and charlock),
(f) methyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, cabbage, cauliflower, brussels sprout, horseradish, and radish),
(g) 4-methylthio-3-butenyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, radish),
(h) 4-pentenyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, horseradish, mustard, turnip, rutabaga, cress, and radish),
(i) 2-phenylethyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, mustard, cabbage, horseradish, watercress, turnip, rapeseed),
(j) phenyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, mustard, spinach, and horseradish),
(k) 6-methylsulfinylhexyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, wasabi),
(l) 3-methylsulfinylpropyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, turnip),
(m) isopropyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, cabbage),
(n) 3-methylthioalkyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, cabbage),
(o) 3-methylsulfonylpropyl isothiocyanate,
(p) 2-hydroxy-3-butenyl isothiocyanate,
(q) sec-butyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, cress),
(r) 4-methylthiobutyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed),
(s) 4-methylpentyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed),
(t) 2-hydroxy-4-pentenyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed),
(u) 5-methylthiopentyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed),
(v) 3-indolylmethyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed),
(w) 4-hydroxy-3-indolylmethyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed),
(x) 1-methoxy-3-indolylmethyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed), and
(y) 4-methoxy-3-indolylmethyl isothiocyanate (which may be synthetically obtained or alternatively naturally obtained from, for example, rapeseed).
Preferred among these isothiocyanate compounds include allyl isothiocyanate, 3-butenyl isothiocyanate, 2-butyl isothiocyanate, p-hydroxybenzyl isothiocyanate, 4-methylthio-3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, 2-phenylethyl isothiocyanate, and phenyl isothiocyanate. Even more preferred among these isothiocyanate compounds include allyl isothiocyanate, 3-butenyl isothiocyanate, 2-butyl isothiocyanate, p-hydroxybenzyl isothiocyanate, and 2-phenylethyl isothiocyanate. Still more preferred among these isothiocyanate compounds include allyl isothiocyanate, 3-butenyl isothiocyanate, and p-hydroxybenzyl isothiocyanate. The most preferred isothiocyanate compound for use in the present invention is p-hydroxybenzyl isothiocyanate. Modes of natural and synthetic preparation of isothiocyanate compounds are set forth herein below.
Non-limiting examples of other isothiocyanate compounds which may be utilized in the products and methods of the present invention include 1-adamantyl isothiocyanate; 1-naphthyl isothiocyanate; 2,4,6-trimethylphenylisothiocyanate; 2,4,6-trichlorophenyl isothiocyanate; 2,4-dichlorophenyl isothiocyanate; 2,4-dimethoxyphenyl isothiocyanate; 2,4-xylyl isothiocyanate; 2,5-dichlorophenyl isothiocyanate; 2,5-difluorophenyl isothiocyanate; 2,5-dimethoxyphenyl isothiocyanate; 2,6-difluorophenyl isothiocyanate; 2,6-dimethylphenyl isothiocyanate; 2-(methylthio)phenyl isothiocyanate; 2-(trifluoromethyl)phenyl isothiocyanate; 2-bromophenyl isothiocyanate; 2-chloro-4-nitrophenyl isothiocyanate; 2-chloro-5-(trifluoromethyl)phenyl isothiocyanate; 2-chloroethyl isothiocyanate; 2-chlorophenyl isothiocyanate; 2-ethylphenyl isothiocyanate; 2-fluorophenyl isothiocyanate; 2-iodophenyl isothiocyanate; 2-methoxy-4-nitrophenyl isothiocyanate; 2-methoxy-5-methylphenyl isothiocyanate; 2-methoxyphenyl isothiocyanate; 2-napthyl isothiocyanate; 2-phenethyl isothiocyanate; 2-phenylethyl isothiocyanate; phenethyl isothiocyanate; 3,3,5-trimethylcycohexyl isothiocyanate; 3,4,5-trimethoxyphenyl isothiocyanate; 3,4-dichlorophenyl isothiocyanate; 3,5-bis(trifluoromethyl)phenyl isothiocyanate; 3,5-di-tert-buryl-4-hydroxyphenyl isothiocyanate; 3,5-dichlorophenyl isothiocyanate; 3-(methylthio)propyl isothiocyanate; 3-(trifluoromethyl)phenyl isothiocyanate; 3-bromophenyl isothiocyanate; 3-chlorophenyl isothiocyanate; 3-cyanophenyl isothiocyanate; 3-fluorophenyl isothiocyanate; 3-methoxyphenyl isothiocyanate; 3-methoxypropyl isothiocyanate; 3-nitrophenyl isothiocyanate; 3-pyridyl isothiocyanate; 4-(methylthio)phenyl isothiocyanate; 4-(trifluoromethyl)phenyl isothiocyanate; 4-bromo-2-chlorophenyl isothiocyanate; 4-bromophenyl isothiocyanate; 4-chlorophenyl isothiocyanate; 4-cyanophenyl isothiocyanate; 4-dimethylamino-1-naphthyl isothiocyanate; 4-ethylphenyl isothiocyanate; 4-fluorophenyl isothiocyanate; 4-iodophenyl isothiocyanate; 4-isopropylphenyl isothiocyanate; 4-methoxyphenyl isothiocyanate; 4-methyl-2-nitrophenyl isothiocyanate; 4-methylphenyl isothiocyanate; 4-nitrophenyl isothiocyanate; 5-chloro-2-methylphenyl isothiocyanate; m-tolyl isothiocyanate; o-tolyl isothiocyanate; p-tolyl isothiocyanate; tert-butyl isothiocyanate; acetyl isothiocyanate; benzoyl isothiocyanate; ethyl isothiocyanate; cyclohexyl isothiocyanate; hexyl isothiocyanate; methallyl isothiocyanate; methyl isothiocyanate; pentyl isothiocyanate; and 2,3-dichlorophenyl isothiocyanate.
In accordance with the present invention it is preferred that the constituent comprising the isothiocyanate compound is an essential oil, natural component of an essential oil, or synthetic component of an essential oil (all as described in more detail hereafter) of any of the Cruciferae family of plants. As is known, the Cruciferae family of plants is a large family having over 3,000 species and about 350 genera. The Cruciferae family of plants is also commonly known by the names Brassicaceae family and/or Brassica family. Alternatively, the constituent comprising the isothiocyanate compound may also be an essential oil, natural component of an essential oil, or synthetic component of an essential oil of any other family of plants which may produce an isothiocyanate compound (through, for example, reaction of myrosinase with a glucosinolate compound; either by natural or synthetic introduction of myrosinase) including, for example, the Resedaceae and Capparidaceae families of plants and, as other non-limiting examples, garlic and onion. Production of isothiocyanate compounds either naturally or synthetically through reaction of myrosinase is discussed herein below.
In this respect, any plant species, and preferably any Cruciferae species which is capable of producing an isothiocyanate compound, may be utilized as the constituent (in the instance of utilizing the essential oil or a natural component of the essential oil) or mimicked to provide the constituent (in the instance of utilizing a synthetic component of the essential oil) in the products of the present invention. The Cruciferae family of plants contains plants such as, for example:
(a) broccoli (including, but not limited to, Brassica oleracea italica),
(b) brussels sprout (including, but not limited to, Brassica oleracea gemmifera),
(c) cabbage (including, but not limited to, Brassica oleracea capitata, Brassica pekinensis, Brassica Chinensis Juslenius (Chinese cabbage), Brassica Chinensis parachinensis, Brassica campestris L. var. chinensis, Brassica Pekinensis, Brassica oleracea L. var. tronchuda, Cheiranthus cheiri, and Iberis sempervirens),
(d) cauliflower (including, but not limited to, Brassica Oleracea var. Botrytis),
(e) charlock,
(f) cole crops,
(g) collards,
(h) cress (including, but not limited to, Lepidium sativum),
(i) horseradish (including, but not limited to, Armoracia rusticana and Armoracia lapathifolia),
(j) kale (including, but not limited to, Chinese kale (Brassica alboglabra), Siberian kale (Brassica napus), Brassica oleracea L. var. botrytis, and Brassica oleracea L. var. gemmifera, 
(k) kohlrabi (also, kholrabi) (including, but not limited to, Brassica oleracea L. var. gongylodes),
(l) mustard (including, but not limited to, brown mustard (Brassica juncea), white mustard (Brassica alba), and black mustard (Brassica nigra)),
(m) nasturium,
(n) radish (including, but not limited to, Raphanus sativus (Chinese radish)),
(o) rapeseed (including, but not limited to, Brassica napus),
(p) rutabaga,
(q) spinach,
(r) turnip (including, but not limited to, Brassica rapa and Brassica campestris L. var. rapifera)
(s) watercress (including, but not limited to, Rorippa nasturtium-aquaticum, Nasturtium officinale, and Barbarea verna),
(t) wasabi (Japanese horseradish) (including, but not limited to, Wasabia japonica and Wasabia tenuis), and
(u) yea-kok-choi (including, but not limited to, Rorippa Indica Hiern).
See e.g., Food Chemistry, Edited by O. R. Fennema, Marcel Dekker, Inc., pp. 602-603 (1985) and Naturally Occurring Antimicrobials in Food, Council for Agricultural Science and Technology, pp. 31-32 (1998).
Preferably, the plant is selected from cabbage, broccoli, brussels sprout, turnip, mustard, watercress, radish, wasabi, horseradish, and rapeseed. More preferably, the plant is selected from mustard and horseradish. Most preferably, the plant is mustard, particularly black mustard or white mustard, most particularly white mustard.
Other non-limiting examples of Cruciferae family plants from which the essential oil may be utilized (in the instance of utilizing the essential oil or a natural component of the essential oil) or mimicked (in the instance of utilizing a synthetic component of the essential oil) according to the present invention include those having a following genera: Acanthocardamum, Aethionema, Agallis, Alliaria, Alyssoides, Alysopsis, Alyssum, Ammosperma, Anastatica, Anchonium, Andrzeiowskia, Anelsonia, Aphragmus, Aplanodes, Arabidella, Arabidopsis, Arabis, Arcyosperma, Armoracia, Aschersoniodoxa, Asperuginoides, Asta, Atelanthera, Athysanus, Aubretia, Aurinia, Ballantinia, Barbarea, Berteroa, Berteroella, Biscutella, Bivonaea, Blennodia, Boleum, Boreava, Bornmuellera, Borodinia, Botscantzevia, Brachycarpaea, Brassica, Braya, Brayopsis, Brossardia, Bunias, Cakile, Calepina, Calymmatium, Camelina, Camelinopsis, Capsella, Cardamine, Cardaminopsis, Cardaria, Carinavalva, Carrichtera, Catadysia, Catenulina, Caulanthus, Caulostramina, Ceratocnemum, Ceriosperma, Chalcanthus, Chamira, Chartoloma, Cheesemania, Cheiranthus (also known as Erisymum), Chlorocrambe, Chorispora, Christolea, Chrysobraya, Chrysochamela, Cithareloma, Clastopus, Clausia, Clypeola, Cochlearia, Coelonema, Coincya, Coluteocarpus, Conringia, Cordylocarpus, Coronopus, Crambe, Crambella, Cremolobus, Cryptospora, Cuphonotus, Cusickiella, Cycloptychis, Cymatocarpus, Cyphocardamum, Dactylocardamum, Degenia, Delpinophytum, Descurainia, Diceratella, Dichasianthus, Dictyophragmus, Didesmus, Didymophysa, Dielsiocharis, Dilophia, Dimorphocarpa, Diplotaxis, Dipoma, Diptychocarpus, Dithyrea, Dolichirhynchus, Dontostemon, Douepea, Draba, Drabastrum, Drabopsis, Dryopetalon, Eigia, Elburzia, Enarthrocarpus, Englerocharis, Eremobium, Eremoblastus, Eremodraba, Eremophyton, Ermania, Ermaniopsis, Erophila, Erucaria, Erucastrum, Euclidium, Eudema, Eutrema, Euzomodendron, Farsetia, Fezia, Fibigia, Foleyola, Fortuynia, Galitzkya, Geococcus, Glaribraya, Glastaria, Glaucocarpum, Goldbachia, Gorodkovia, Graellsia, Grammosperma, Guiraoa, Gynophorea, Halimolobos, Harmsiodoxa, Hedinia, Heldreichia, Heliophila, Hemicrambe, Hemilophia, Hesperis, Heterodraba, Hirschfeldia, Hollermayera, Hornungia, Hornwoodia, Hugueninia, Hymenolobus, Iberis, Idahoa, Iodanthus, Ionopsidium, Irenepharsus, Isatis, Ischnocarpus, Iskandera, Iti, Ivania, Kernera, Kremeriella, Lachnocapsa, Lachnoloma, Leavenworthia, Lepidium, Lepidostemon, Leptaleum, Lesquerella, Lignariella, Lithodraba, Lobularia, Lonchophora, Loxostemon, Lunaria, Lyocarpus, Lyrocarpa, Macropodium, Malcolmia, Mancoa, Maresia, Mathewsia, Matthiola, Megacarpaea, Megadenia, Menkea, Menonvillea, Microlepidium, Microsysymbrium, Microstigma, Morettia, Moricandia, Moriera, Morisia, Murbeckiella, Muricaria, Myagrum, Nasturtiopsis, Nasturtium (also known as Rorippa), Neomartinella, Neotchihatchewia, Neotorularia, Nerisyrenia, Neslia, Neuontobotrys, Notoceras, Notothlaspi, Ochthodium, Octoceras, Onuris, Oreoloma, Oreophyton, Ornithocarpa, Orychophragmus, Otocarpus, Oudneya, Pachycladon, Pachymitus, Pachyphragma, Pachypterygium, Parlatoria, Parodiodoxa, Parolinia, Parrya, Parryodes, Pegaeophyton, Peltaria, Peltariopsis, Pennellia, Petiniotia, Petrocallis, Phaeonychium, Phleholobium, Phlegmatospermum, Phoenicaulis, Physaria, Physocardamum, Physoptychis, Physorrhynchus, Platycraspedum, Polyctenium, Polypsecadium, Pringlea, Prionotrichon, Pritzelago, Pseuderucaria, Pseudocamelina, Pseudoclausia, Pseudofortuynia, Pseudovesicaria, Psychine, Pterygiosperma, Pterygostemon, Pugionium, Pycnoplinthopsis, Pycnoplinthus, Pyramidium, Quezeliantha, Quidproquo, Raffenaldia, Raphanorhyncha, Raphanus, Rapistrum, Rehoudia, Redowskia, Rhizobotrya, Ricotia, Robeschia, Rollinsia, Romanschulzia, Roripella, Rytidocarpus, Sameraria, Sarcodraba, Savignya, Scambopus, Schimpera, Schivereckia, Schizopetalon, Schlechteria, Schoenocrambe, Schouwia, Scoliaxon, Selenia, Sibara, Silicularia, Sinapidendron, Sinapis, Sisymbrella, Sisymbriopsis, Sisymbrium, Smelowskia, Sobolewslia, Sohms-Laubachia, Sophiopsis, Sphaerocardamum, Spirorhynchus, Spryginia, Staintoniella, Stanfordia, Stanleya, Stenopetalum, Sterigmostemum, Stevenia, Straussiella, Streptanthella, Streptanthus, Streptoloma, Stroganowia, Stubebdorffia, Subularia, Succowia, Synstemon, Synthlipsis, Taphrospermum, Tauscheria, Teesdalia, Teesdaliopsis, Tetracme, Thelypodiopsis, Thelypodium, Thlaspeocarpa, Thlaspi, Thysanocarpus, Trachystoma, Trichotolinum, Trochiscus, Tropidocarpum, Turritis, Vella, Warea, Weberbauera, Werdermannia, Winklera, Xerodraba, Yinshania, Zerdana, and Zilla.
In accordance with the present invention, it is preferred to utilize an essential oil or, most preferably a natural component thereof, as a constituent of the present products; wherein such is utilized the products may readily be utilized in food and beverage products. Wherein an essential oil, or natural component thereof, is utilized as a constituent of the present products, the oil is preferably derived from a plant which is a member of the Cruciferae family; non-limiting examples of such members are stated above. As used herein, xe2x80x9cessential oilxe2x80x9d refers to the set of all the compounds that can be distilled from the plant from which the oil is derived and that contributes to the characteristic aroma of that plant. See e.g., H. McGee, On Food and Cooking, Charles Scribner""s Sons, p. 154-157 (1984). In accordance with the present invention, the essential oil preferably originates from a glucosinolate compound which is capable of producing an isothiocyanate compound (for example, through the catalytic hydrolysis of one or more glucosinolates by the enzyme myrosinase) wherein the precursor and enzyme containing plant tissue is homogenized, ground, crushed, pressed, or otherwise damaged. The essential oil derived from a Cruciferae family plant is obtained using procedures which are commonly known in the art.
As is known in the art, the seeds and/or flowers (preferably seeds) of any of, for example, a Cruciferae species, may be, homogenized, ground, crushed, pressed, or otherwise damaged to activate one or more precursors (e.g., glucosinolates) of the corresponding essential oil. Isothiocyanate compound production from the oil is known to occur by enzyme catalysis upon, for example, homogenizing, grinding, crushing, pressing, or otherwise damaging the plant, seed and/or flower thereof. See e.g., Concannon, WO 94/01121, published Jan. 20, 1994 and Brown et al., xe2x80x9cGlucosinolate-Containing Plant Tissues as Bioherbicidesxe2x80x9d, Journal of Agricultural Food Chemistry, Vol. 43, pp. 3070-3074 (1995). The enzyme commonly known to participate in the production of the isothiocyanate compound upon interaction with a glucosinolate is myrosinase, which is also known as thioglucoside glucohydrolase (and having enzyme classification number EC 3.2.3.1). Myrosinase is known to be non-specific for various glucosinolates.
The essential oil may be obtained from any of a variety of known methods. For example, the plant utilized may be homogenized, ground, crushed, pressed, or otherwise damaged (e.g., cut); the essential oil may then be extracted using a volatile organic solvent, for example, an alcohol (e.g., methanol) or diethyl ether, or a compound such as propylene glycol. See e.g., Ono et al., xe2x80x9c6-Methylsulfinylhexyl Isothiocyanate and Its Homologues as Food-originated Compounds with Antibacterial Activity against Escherichia coli and Staphylococcus aureusxe2x80x9d, Bioscience, Biotechnology, and Biochemistry, Vol. 62(2), pp. 363-365 (1998). Alternatively, the essential oil may be obtained via distillation (for example, steam distillation depending upon the volatility of the isothiocyanate compound present therein) after homogenizing, grinding, crushing, pressing, or otherwise damaging the plant, seed, flower, and/or any other component thereof. See e.g., Isshiki et al., xe2x80x9cPreliminary Examination of Allyl Isothiocyanate Vapor for Food Preservationxe2x80x9d, Bioscience, Biotechnology, and Biochemistry, Vol. 56(9), pp. 1476-1477 (1992). As another non-limiting example, the plant, seed, flower, and/or any other component thereof, may be centrifuged with water.
The essential oil itself, which contains one or more isothiocyanate compounds, may then be utilized in the products and methods of the present invention.
Alternatively, a natural component of the essential oil may be utilized. As used herein, the term xe2x80x9cnatural componentxe2x80x9d, with reference to the corresponding essential oil, refers to a component utilized in the present invention which is obtained from the naturally occurring essential oil. The essential oil is preferably of a Cruciferae family plant. As stated herein above, the natural component of the essential oil should comprise one or more isothiocyanate compounds (i.e., a compound bearing a xe2x80x94Nxe2x95x90Cxe2x95x90S moiety).
The method by which the natural component is obtained from the essential oil is not critical to the present invention. According to the present invention, the natural component should comprise one or more isothiocyanate compounds and may optionally comprise further components derived from the essential oil. To illustrate, the natural component of the essential oil may be obtained through standard purification of the essential oil itself to obtain one or more isothiocyanate compounds using, for example, extraction, chromatography, or distillation. For example, common chromatography techniques (e.g., HPLC) may be utilized to obtain a natural component of the essential oil. See e.g., Ono et al., xe2x80x9c6-Methylsulfinylhexyl Isothiocyanate and Its Homologues as Food-originated Compounds with Antibacterial Activity against Escherichia coli and Staphylococcus aureusxe2x80x9d, Bioscience, Biotechnology, and Biochemistry, Vol. 62(2), pp. 363-365 (1998). As a further example, an essential oil once distilled (the essential oil itself) may again be distilled to remove volatile components not of interest or to remove the isothiocyanate compound of interest. It is a preferred embodiment of the present invention to utilize a natural component of the essential oil.
Alternative to utilizing the essential oil or natural component thereof in the present invention, a synthetic component of an essential oil, preferably a Cruciferae essential oil, may be utilized. As used herein, the term xe2x80x9csynthetic componentxe2x80x9d with reference to the corresponding essential oil refers to a component utilized in the present invention which naturally occurs in an essential oil which has been activated through myrosinase, but which is rather obtained through synthetic techniques without extraction or purification from a naturally occurring essential oil. As stated herein above, the synthetic component of the essential oil should comprise one or more isothiocyanate compounds (i.e., a compound bearing a xe2x80x94Nxe2x95x90Cxe2x95x90S moiety).
A variety of synthetic isothiocyanate compounds may be commercially obtained, for example, from Aldrich Chemical Co., Milwaukee, Wis.; Fluka Chemical Co., Milwaukee, Wis.; Sigma Chemical Co., St. Louis, Mo.; and Lancaster Synthesis Inc., Windham, N.H. Additionally, synthetic methods of preparing isothiocyanate compounds are well-known in the art. See e.g., J. March, Advanced Organic Chemistry, John Wiley and Sons (1992). Additionally, natural production of isothiocyanate compounds may be synthetically mimicked by commercially obtaining one or more glucosinolate compounds and introducing myrosinase which may be isolated from any myrosinase producing plant (as discussed above) or commercially obtained (for example, myrosinase is commercially available as thioglucosidase from Sigma Chemical Co., St. Louis, Mo.). Alternatively, natural production of isothiocyanate compounds may be synthetically mimicked by isolating a glucosinolate compound from any glucosinolate producing plant and introducing myrosinase which is commercially obtained.
The following non-limiting examples demonstrate methods of obtaining the isothiocyanate compound, either as the essential oil, a natural component thereof, or synthetic component thereof: